CN101532141B - Method for in situ producing aluminide reinforced layer on surface of aluminum alloy - Google Patents
Method for in situ producing aluminide reinforced layer on surface of aluminum alloy Download PDFInfo
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- CN101532141B CN101532141B CN2009100204883A CN200910020488A CN101532141B CN 101532141 B CN101532141 B CN 101532141B CN 2009100204883 A CN2009100204883 A CN 2009100204883A CN 200910020488 A CN200910020488 A CN 200910020488A CN 101532141 B CN101532141 B CN 101532141B
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Abstract
The invention relates to a method for producing an intermetallic aluminide composite reinforced layer on the surface of an aluminum alloy, and belongs to the technical field of material processing. The method comprises the following steps: mixing nickel-titanium alloy powder and polyvinyl alcohol solution in a certain proportion; spraying the mixture on the surface of an aluminum alloy substrate; and obtaining an aluminum alloy substrate attached to a reinforced layer by using laser scanning. The reinforced layer prepared by the method does not produce cracking and can greatly improve the wear-resisting property of the aluminum alloy.
Description
Technical field
The present invention relates to a kind of method, belong to the material processing technical field at aluminum alloy surface original position generation intermetallic aluminide complex intensifying layer.
Technical background
Aluminium alloy is owing to have higher specific tenacity and good corrosion resisting property and obtained widespread use in industry in atmosphere.Only be example, its parts such as cylinder body, cylinder head, piston, wheel, inlet pipe, bearing circle, transmission case, clutch housing, shake wall cover, oil pump casing, scatterer, oil cooler, vaporizer, condenser, floor and support etc. and all adopt aluminium alloy to make with the automobile.Yet the hardness of aluminium alloy is on the low side, wear no resistance, and the anti-corrosion and resistance toheat under some operating mode is also undesirable, and this has not only influenced the work-ing life of aluminium alloy part, has also restricted its application in the related industries field.Because aluminium alloy can not increase substantially its strong hardness by phase transformation, so thermal treatment can not make its wear resisting property significantly improve.Carry out laser treatment again behind the powdered alloy of the pre-metallize of aluminum alloy surface, then not only can significantly strengthen wear resisting property, and corrosion resisting property is improved, this construction and development to national economy has crucial meaning.
Aluminum alloy surface prepares the existing many reports of research of wear-resistant coating.The America and Europe just began one's study in aluminum alloy surface spraying of wearable coating technology the nineties in 20th century.U.S. Sandia government test chamber and GM company are once in the life-span of aluminium alloy engine cylinder wall spraying of wearable coating with the raising body.The people such as Bialucki of Poland adopt plasma spraying technology to spray Ni-based on the alloy matrix aluminum after the process sandblast and result iron alloy coating shows that coating and high base strength are lower, are about 20Mpa.Referring to Piotr Bialucki, et al.Study of adhesion of different plasma-sprayed coatings to aluminium.Surface and Coatings Technology.2006,201 (5): 2061-2064.And the ZL101 alloy substrate is adopted its bonding strength of Ni-Cr alloy coat of hot-spraying techniques preparation only is about 8.3MPa.Referring to Zhao Wen cross board at the rear of an ancient carriage etc., the bonding strength of aluminium surface laser cladding hard alloy layer. Arms Material scientific and engineering, 1997,20 (1): 41-46.Ceramic film and high base strength height that aluminium alloy forms through the differential arc oxidation rear surface, hardness can reach 2500HV.Referring to Li Jinfu etc., the wear resistance of Micro-Arc Oxidized Ceramic Layer of Aluminum Alloy. University of Science ﹠ Technology, Beijing's journal, 2003,25 (6): 542-544.Xue Wenbin etc., the abrasion resistance of LY12 alloy surface differential arc discharge depositing ceramic membrane. Beijing Normal University's journal, 2005,41 (4): 380-382.But differential arc oxidation film top layer is loose, and dry friction coefficient big (0.68-0.86), moreover resultant all is a ceramic phase, and rete fragility is bigger, should not bear big shock load.Referring to hot iron prop etc., the tribological property of aluminum alloy surface ceramic coating formed by micro-arc oxidation and Study on Microstructure. space flight manufacturing technology, 2005, (4): 5-8.Fanya?Jin，et?al.Improvement?of?surface?porosity?and?properties?ofalumina?films?by?incorporation?of?Fe?micrograins?in?micro-arc?oxidation.Applied?SurfaceScience，2006，253(2)：863-868。To adopting ion implantation technique and plasma glow discharge nitrogenize technology to show in the test result of the AlN strengthening layer of aluminum alloy surface formation, its hardness can reach 1200HV, and wear rate and frictional coefficient are all reduced, yet its shortcoming is rete thin (＜10 μ m), and its work-ing life is still undesirable under the frrction load effect.Referring to P.Vissutipitukul, et al.Wear of plasma-nitrided aluminum alloys.Wear, 2005,259 (1-6): 482-489.J.Jagielski，et?al.Werner.Effects?of?high?dose?nitrogen?implantation?into?aluminum.Vacuum，2003，70(2-3)：147-152。Yun-Keun?Shim，et?al.The?properties?of?AlN?prepared?by?plasma?nitriding?andplasma?source?ion?implantation?techniques.Surface?and?Coatings?Technology，2000，131(1-3)：345-349。
Utilizing laser that material is carried out surface modification is one of focus of domestic and international material surface engineering field research at present.The laser beam of high-energy-density can carry out modification to the particular surface of workpiece in a short period of time to be handled.The nonequilibrium process of rapidly solidification can form compound and the supersaturated solid solution that common alloyage process is difficult to obtain, the strengthening layer of obtained performance excellence.By reasonably combined reinforcement constituent element with optimize processing parameter, the performance such as wear-resisting, anti-corrosion, heat-resisting and anti-oxidant of strengthening layer is all improved.On the other hand, because laser reinforcing layer and body material form metallurgical binding, its intensity is far above the sprayed coating of mechanical bond.Compare with thermals source such as electron beams, laser treatment needing no vacuum working spaces, whether processed workpiece conducts electricity is not all had influence.
It mainly is to form the complex intensifying layer to improve its wear resisting property by ceramic phases such as cladding carbide and borides that forefathers carry out laser surface intensified research to aluminium alloy.Man etc. once adopted the induced with laser synthetic technology to prepare the strengthening layer that contains WC and TiC in aluminum alloy surface, and test result shows that its wear rate is reduced to 1/6 of matrix.Referring to H.C.Man, et al.Laserinduced reaction synthesis of TiC+WC reinforced metal matrix composites coatings onAl6061.Surface and Coatings Technology, 2004,185 (1): 74-80.H.C.Man，et?al.In?situ?synthesisof?TiC?reinforced?surface?MMC?on?Al6061?by?laser?surface?alloying.Scripta?Materialia，2002，46(3)：229-234。S.Tomida，et?al.Formation?of?metal?matrix?composite?layer?on?aluminum?alloywith?TiC-Cu?powder?by?laser?surface?alloying?process.Surface?and?Coatings?Technology，2001，142-144：585-589。Yet Dubourg etc. studies show that, along with increasing of carbide content in the laser reinforcing layer, its wear resisting property is the enhanced while gradually, and the crack number in the strengthening layer also increases thereupon.Referring to L.Dubourg, et al.Cornet.Laser cladding of MMC coatings on aluminium substrate:influence of composition andmicrostructure on mechanical properties.Wear, 2005,258 (11-12): 1745-1754.P.H.Chong，et?al.Microstructure?and?wear?properties?of?laser?surface-cladded?Mo-WC?MMC?on?AA6061?aluminumalloy.Surface?and?Coatings?Technology，2001，145(1-3)：51-59。P.H.Chong，et?al.Laserfabrication?of?Mo-TiC?MMC?on?AA6061?aluminum?alloy?surface.Surface?and?CoatingsTechnology，2002，154(2-3)：268-275。L.Dubourg，H.Pelletier，D.Vaissiere，F.Hlawka，A.Cornet.Mechanical?characterisation?of?laser?surface?alloyed?aluminium-copper?systems.Wear，2002，253(9-10)：1077-1085。
Studies show that TiB what aluminum alloy surface laser prepared boride complex intensifying layer
2Deng boride wear resisting property is improved significantly, but the aluminium alloy solidity to corrosion is descended, and easily produce coating cracking.Referring to Jiang Xu, et al.Wear characteristicof in situ synthetic TiB
2Particulate-reinforoed Al matrix composite formed by laser cladding.Wear, 2006,260 (4-5): 486-492.Jiang?Xu，et?al.Microstructure?and?wear?properties?of?laser?claddingTi-Al-Fe-B?coatings?on?AA2024?aluminum?alloy.Materials?and?Design，2006，27(5)：405-410。J.Dutta?Majumdar，et?al.In?situ?dispersion?of?titanium?boride?on?aluminium?by?laser?compositesurfacing?for?improved?wear?resistance.Surface?and?Coatings?Technology，2006，201(3-4)：1236-1242。
Not only wear resisting property raising behind the aluminium alloy via nitride, and strengthened against corrosion and resistance of oxidation.Referring to H.-Y.Chen, etal.Plasma-assisted nitriding of aluminum.Surface and Coatings Technology, 1994,64 (3): 139-147.W.Biller，et?al.Modification?of?steel?and?aluminium?by?pulsed?energetic?ion?bearms.Surface?and?Coatings?Technology，1999，116-119：537-542。Yoshihito?Hara，et?al.AlN?formationand?enhancement?of?high-temperature?oxidation?resistance?by?plasma-based?ionimplantation.Surface?and?Coatings?Technology，2003，169-170：359-362。But Carpnen etc. studies show that, easily form behind the aluminium alloy via nitride that AlN content is lower than inside in the top layer, thereby can not obtain the ideal surface property, and this also is that forefathers study lessly to the aluminium alloy nitride laser one of reason.Referring to E.Carpene, et al.Laser nitriding ofiron and aluminum.Applied Surface Science, 2002,186 (1-4): 100-104.A.L.Thomann，et?al.Surface?nitriding?of?titanium?and?aluminium?by?laser-induced?plasma.Surface?and?CoatingsTechnology，1997，97(1-3)：448-452。
The intermetallic compound of formation such as aluminium and titanium, nickel all has higher modulus of elasticity and strong hardness, good against corrosion and high-temperature behavior.Referring to Qi Xinzhe etc., aluminium alloy and aluminide coating current situation. mechanical engineering material, 2005,26 (6): 4-7.S.C.Deevi，et?al.Nickel?and?iron?aluminides：an?overview?on?properties，processing，and?applications.Intermetallics，1996，4(5)：357-375。Chen Ziqiang. intermetallic compound and application thereof. Shanghai non-ferrous metal, 2005,26 (4): 191-196.Utilize Al
3The matrix material of Ti and ZL101 preparation not only tensile strength, hardness and elongation obviously improves than the ZL101 matrix, and frictional coefficient and also obviously reduction of wear rate.And Ni
3Al base coating then makes the anticorrosive and oxidation capacity of alloy matrix aluminum all significantly be strengthened, and the coating and the matrix bond of formation are better, and do not have cracking phenomena.Referring to Al such as Zhao Yuhou
3Wild phase Al in the Ti/ZL101 in-situ composite
3Ti structure and strengthening mechanism. heat processing technique, 2002, (5): 47-49.M.D.Salvador，et?al.Microstructure?and?mechanical?behaviour?of?Al-Si-Mg?alloys?reinforced?with?Ti-Alintermetallics.Journal?of?Materials?Processing?Technology，2003，143-144：605-611。Debdas?Roy，et?al.Tribological?properties?of?Ti-aluminide?reinforced?Al-based?in?situ?metal?matrixcomposite.Intermetallics，2005，13(7)：733-740。Buta?Singh?Sidhu，et?al.Evaluation?of?thecorrosion?behaviour?of?plasma-sprayed?Ni
3Al?coatings?on?steel?in?oxidation?and?molten?saltenvironments?at?900℃.Surface?and?Coatings?Technology，2003，166(1)：89-100。J.L.He，et?al.Acomparative?study?of?the?cyclic?thermal?oxidation?of?PVD?nickel?aluminide?coatings.Surface?andCoatings?Technology，2002，155(1)：67-79。
From the above, intermetallic aluminide not only has higher hardness and good corrosion resisting property, and with alloy matrix aluminum better avidity is arranged.But the ceramic reinforced layer cracking phenomena appears in existing laser surface intensified aluminium alloy technology easily, influences the quality and the quality of product.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, a kind of method at aluminum alloy surface original position generation intermetallic aluminide complex intensifying layer is provided, the strengthening layer that is prepared by this method does not produce cracking, can significantly improve the wear resisting property of aluminium alloy.
A kind of method at aluminum alloy surface original position generation aluminide reinforced layer, step is as follows:
1) with granularity be 200 purpose nickel by powder and ti powder, with mass ratio Ni: Ti=1: 1.2～1: 1.5 uniform mixing, the Ni-Ti alloy powder;
2) polyvinyl alcohol is mixed with volume ratio with water at 1: 6, get mixed solution;
3) the Ni-Ti alloy powder and the step 2 that step 1) are made) mixed solution that makes is with 1: 4 mixing of mass ratio, spray coating liquor, with spray gun spray coating liquor is sprayed at the aluminum alloy base material surface, 100～150 ℃ of oven dry 0.5～1h;
4) adopting wavelength is that the solid continuous laser folk prescription of 1.06 μ m is to scanning step 3) aluminum alloy surface handled, this solid continuous laser output rating is 1000～3000 watts, spot diameter 1～4mm, sweep velocity 10～15mm/s, overlapping rate is 30%, with the coaxial argon gas that is blown into of laser beam, ar pressure is 0.3MPa.At the generated in-situ intermetallic aluminide strengthening layer of aluminum alloy surface as shown in Figure 1.Overlapping rate is meant that the overlapping area between the adjacent twice laser scanning track accounts for the per-cent of the total area.
Adopting wavelength in this step 4) is that the solid continuous laser of 1.06 μ m is than CO
2Little 1 order of magnitude of the wavelength of gas laser, light beam are beneficial to aluminium alloy and absorb, thereby Solid State Laser is more suitable for the Laser Surface Treatment of aluminium alloy, are blown into argon gas and avoid oxidation with the protection laser molten pool.
Above-mentioned steps 3) in, the spray coating liquor coating thickness is 0.1～0.2mm.
Beneficial effect of the present invention is as follows:
1, the strengthening layer of Xing Chenging can make the strong hardness of aluminum alloy surface and wear resisting property greatly improve; Strengthening layer hardness ratio alloy matrix aluminum hardness improves 2-3 doubly.
2, intermetallic aluminide and aluminium alloy consistency are good, and strengthening layer does not produce cracking and peels off defective.
3, production technique of the present invention is simple and easy to do, the strengthening layer steady quality.
Description of drawings
Fig. 1 is 3000 watts of output ratings, the strengthening layer that forms after the laser scanning of spot diameter 4mm;
Fig. 2 is 1000 watts of output ratings, the strengthening layer that forms after the laser scanning of spot diameter 1mm;
Fig. 3 is an embodiment 1XRD atlas analysis;
Fig. 4 is embodiment 1 a Vickers' hardness impression;
Fig. 5 is 3000 watts of output ratings, the wear testing result of the strengthening layer that forms after the laser scanning of spot diameter 4mm;
Fig. 6 is embodiment 1 alloy matrix aluminum wear testing result.
Embodiment
Below in conjunction with Figure of description, the present invention is further elaborated, institute of the present invention protection domain is not limited thereto.
Described various raw materials of present embodiment and reagent are the commercially available prod, and selected laser apparatus is TrumpfHL 4000D (4000W) and Rofin-Sinar CW 020 (2000W) Nd:YAG solid statelaser.
Embodiment 1
A kind of method at aluminum alloy surface original position generation aluminide reinforced layer, step is as follows:
1) with granularity be 200 purpose nickel by powder and ti powder, with mass ratio Ni: Ti=1: 1.5 uniform mixing, the Ni-Ti alloy powder;
2) polyvinyl alcohol is mixed with volume ratio with water at 1: 6, get mixed solution;
3) the Ni-Ti alloy powder and the step 2 that step 1) are made) mixed solution that makes is with 1: 4 mixing of mass ratio, spray coating liquor, with spray gun spray coating liquor is sprayed at the aluminum alloy base material surface, the spray coating liquor coating thickness is 0.1mm, 100 ℃ of oven dry 1h;
4) adopting wavelength is the solid continuous laser of 1.06 μ m, and output rating is 3000 watts, spot diameter 4mm, sweep velocity 10mm/s, overlapping rate are 30%, with the coaxial argon gas that is blown into of laser beam, ar pressure is 0.3MPa, folk prescription to scanning above-mentioned steps 3) oven dry after the aluminum alloy base material surface.
The strengthening layer that forms after the laser scanning as shown in Figure 1.Learn that by the XRD figure spectrum analysis original position has formed NiAl, AlTi, Al in the strengthening layer
3Strengthening phases such as Ti, as shown in Figure 3.Fig. 4 is the Vickers' hardness impression of present embodiment product, and by this photo as can be seen, strengthening layer combines well with alloy matrix aluminum, and strengthening layer hardness average is 318.3HV, is much higher than alloy matrix aluminum hardness 102.2HV.
Wearing test
The MPX-2000 dish pin formula friction and wear test machine (through improving) that utilizes Xuanhua experimental machine Manufacturing Co., Ltd to produce carries out wearing test, load: 2kg; Rotation radius: 20mm; Rotating speed: 200rpm; Time: 5min, the strengthening layer wear results as shown in Figure 5, twice wear weight loss average is 0.34g.The alloy matrix aluminum wear results as shown in Figure 6, twice wear weight loss average is 1.47g.
Embodiment 2
As embodiment 1 described a kind of method that generates aluminide reinforced layer in the aluminum alloy surface original position, difference is, in the step 1), Ni in the Ni-Ti alloy powder: the Ti mass ratio is 1: 1.2, in the step 4), laser output power is 1000 watts, spot diameter 1mm, and the strengthening layer that the scanning back forms is as shown in Figure 2.Strengthening layer combines with alloy matrix aluminum well, and strengthening layer hardness average is 319.4HV.
Claims (1)
1. one kind generates the method for aluminide reinforced layer in the aluminum alloy surface original position, it is characterized in that step is as follows:
1) with granularity be 200 purpose nickel by powder and ti powder, with mass ratio Ni: Ti=1: 1.2～1: 1.5 uniform mixing, the Ni-Ti alloy powder;
2) polyvinyl alcohol is mixed with volume ratio with water at 1: 6, get mixed solution;
3) the Ni-Ti alloy powder and the step 2 that step 1) are made) mixed solution that makes is with 1: 4 mixing of mass ratio, spray coating liquor, with spray gun spray coating liquor is sprayed at the aluminum alloy base material surface, the spray coating liquor coating thickness is 0.1～0.2mm, 100～150 ℃ of oven dry 0.5～1h;
4) adopting wavelength is that the solid continuous laser folk prescription of 1.06 μ m is to scanning step 3) aluminum alloy surface handled, this solid continuous laser output rating is 1000～3000 watts; Spot diameter 1～4mm, sweep velocity 10～15mm/s, overlapping rate are 30%, with the coaxial argon gas that is blown into of laser beam, ar pressure is 0.3MPa.
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| CN102031515B (en) * | 2010-12-09 | 2012-07-11 | 华中科技大学 | Laser alloying process for cylinder liner inner wall |
| CN101985751B (en) * | 2010-12-10 | 2012-05-23 | 云南昆钢联合激光技术有限公司 | Motor mandrel surface strengthening layer compound technology |
| CN104328431A (en) * | 2014-11-14 | 2015-02-04 | 重庆理工大学 | Aluminum alloy surface modification method |
| CN104388927B (en) * | 2014-11-14 | 2017-01-18 | 重庆理工大学 | Method for preparing high-hardness coating on aluminum alloy surface |
| CN104357838B (en) * | 2014-11-14 | 2017-01-25 | 重庆理工大学 | Method for refining silicide phase in multi-principal-element alloy coating |
| CN105112697A (en) * | 2015-07-27 | 2015-12-02 | 兰州理工大学 | (Ti@A13Ti)p/Al-based in-situ composite material powder thixo-forming method |
| CN108342730B (en) * | 2018-04-03 | 2020-02-14 | 大连大学 | NiTi alloy visible under X-ray and preparation method thereof |
| CN108796498B (en) * | 2018-05-28 | 2020-06-09 | 江苏大学 | Method for generating ceramic phase by laser cladding aluminum alloy surface self-reaction |
| CN112920687B (en) * | 2021-03-01 | 2022-06-10 | 西北永新涂料有限公司 | Single-component flake type epoxy zinc-rich anti-corrosive primer and preparation method thereof |
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| CN101012561A (en) * | 2007-02-01 | 2007-08-08 | 天津工业大学 | Aluminum alloy surface strengthening method using laser melting and coating |
| CN101265576A (en) * | 2008-05-07 | 2008-09-17 | 哈尔滨工业大学 | Ceramic granule enhanced method for aluminum or aluminum alloy surface |
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| CN101012561A (en) * | 2007-02-01 | 2007-08-08 | 天津工业大学 | Aluminum alloy surface strengthening method using laser melting and coating |
| CN101265576A (en) * | 2008-05-07 | 2008-09-17 | 哈尔滨工业大学 | Ceramic granule enhanced method for aluminum or aluminum alloy surface |
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